We report comparative structural changes of potassium-contained zeolite-W (K-MER, structural analogue of natural zeolite merlinoite) and monovalent extra-framework cation (EFC)-exchanged M-MERs (M = Li+, Na+, Ag+, and Rb+). High-resolution synchrotron X-ray powder diffraction study precisely determines that crystal symmetry of MERs is tetragonal (I4/mmm). Rietveld refinement results reveal that frameworks of all MERs are geometrically composed of disordered Al/Si tetrahedra, bridged by linkage oxygen atoms. We observe a structural relationship between a group of Li-, Na-, and Ag-MER and the group of K- and Rb-MER by EFC radius and position of M(1) site inside double 8-membered ring unit (d8r). In the former group, a-axes decrease reciprocally, c-axes gradually extend by EFC size, and M(1) cations are located at the middle of the d8r. In the latter group, a- and c-axes lengths become longer and shorter, respectively, than axes of the former group, and these axial changes come from middle-to-edge migration of M(1) cations inside the d8r channel. Unit cell volumes of the Na-, Ag-, and K-MER are ca. 2005 Å3, and the volume expansion in the MER series is limited by EFC size, the number of water molecules, and the distribution of extra-framework species inside the MER channel. EFC sites of M(1) and M(2) show disordered and ordered distribution in the former group, and all EFC sites change to disordered distribution after migration of the M(1) site in the latter group. The amount of water molecules and porosities are inversely proportional to EFC size due to the limitation of volume expansion of MERs. The channel opening area of a pau composite building unit and the amount of water molecules are universally related as a function of cation size because water molecules are mainly distributed inside a pau channel.
Keywords: Rietveld refinement; cation form; synchrotron X-ray diffraction; zeolite-W.